CN110746375B - 一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及应用 - Google Patents
一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及应用 Download PDFInfo
- Publication number
- CN110746375B CN110746375B CN201810830434.2A CN201810830434A CN110746375B CN 110746375 B CN110746375 B CN 110746375B CN 201810830434 A CN201810830434 A CN 201810830434A CN 110746375 B CN110746375 B CN 110746375B
- Authority
- CN
- China
- Prior art keywords
- thiadiazin
- thio
- acethydrazide
- phenyl
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/15—Six-membered rings
- C07D285/16—Thiadiazines; Hydrogenated thiadiazines
- C07D285/34—1,3,5-Thiadiazines; Hydrogenated 1,3,5-thiadiazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
本发明属于农药杀菌剂领域,公开了一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及应用,该类化合物的结构如式(I)所示:
Description
技术领域
本发明涉及农药杀菌剂领域,具体涉及一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及其在防治植物真菌病害方面的应用,具有制备农药杀菌剂的用途。
背景技术
噻二嗪硫酮类衍生物是一种含有1,3,5-噻二嗪-2-硫酮结构的含氮含硫杂环化合物,该类化合物常常显示出杀菌、抑霉、杀虫和抗病毒活性。代森环(milneb)是一种含有噻二嗪硫酮结构的杀菌剂,具有广谱杀菌作用,可用于防治蔬菜及果树上的多种病害,对瓜类和白菜的霜霉病和小麦锈病的防治效果也较为显著。绵隆(dazomet)同样是一种具有噻二嗪硫酮结构的杀菌剂,适用于白菜、黄瓜、玉米、马铃薯和番茄等植物上病害的防治,不仅可作为杀真菌剂使用,还可用于除草及杀线虫等。
酰肼类化合物常具有良好的杀菌、杀虫等活性。含酰肼基团的杀菌剂叶枯灵(saikuzuo)是一种高效杀菌剂,具有保护和内吸治疗作用,可用于防治水稻白叶枯病、西红柿早晚疫病、马铃薯晚疫病和黄瓜疫病、炭疽病等。抑食肼(RH-5849)是一种常用的酰肼类昆虫生长调节剂,该化合物具有优异的蜕皮激素活性,被广泛应用于甜菜夜蛾(Spodopteraexigua Hübner)等鳞翅目害虫的防治。Zareef等设计合成的含有酰肼结构的磺酰胺类化合物对白色念珠菌(Candida albicans)具有良好的抑制效果(Eur.J.Med.Chem,2008,141-52.)。Yu X合成的一类含有酰肼结构的香豆素衍生物对水稻纹枯病菌(Rhizoctorziasolani)具有显著的抑制活性(Fitoterapia,2018,127:387-95.)。
本发明在5-取代的噻二嗪硫酮的3位引入取代乙酰苯肼结构,设计并合成了一种含噻二嗪硫酮基团的乙酰苯肼类化合物,发现该类化合物具有显著的杀菌活性。
发明内容
本发明的目的在于,提供一种含噻二嗪硫酮基团的乙酰苯肼类化合物。
本发明的另一目的在于提供一种含噻二嗪硫酮基团的乙酰苯肼类化合物的制备方法。
本发明还有一个目的在于提供上述化合物的用途。
本发明的第一方面提供了一种具有通式(I)所示结构的一种含噻二嗪硫酮基团的乙酰苯肼类化合物,
在式(I)中,所述各个基团具有如下所述的定义:
R1选自H、C1-6烷基、苯基、取代苯基、苯甲基、取代苯甲基,所述的取代基团选自1-3个卤素、1-2个C1-6烷基;
R2选自H、C1-6烷基、苯基、取代苯基、苯甲基、取代苯甲基,所述的取代基团选自1-3个卤素、1-2个C1-6烷基;
Y(n)中,n=1-5取代,Y(n)选自下列1-5个基团:H、X、R’、OR”、NO2,其中X表示卤素;R’表示未取代或被1个或多个卤素取代的C1-6烷基;R”表示氢、未取代或被1个或多个卤素取代的C1-6烷基。
在式(I)中,所述各个基团具有如下所述的进一步优选定义:
R1选自C1-6烷基、苯基、取代苯基、苯甲基,所述的取代基团选自1-3个卤素;
R2选自H、C1-6烷基;
Y(n)中,n=1-3取代,Y(n)选自下列1-3个基团:H、F、Cl、Br、C1-6烷基、OC1-6烷基、1-5个卤素取代的C1-6烷基。
在式(I)中,所述各个基团具有如下所述的更进一步优选定义:
R1选自CH3、苯基、4-氟苯基、苯甲基;
R2选自H、CH3;
Y(n)选自H、2-F、4-F、2-Cl、3-Cl、4-Cl、4-Br、2,4-(Cl)2、2,4,6-(Cl)3、4-CH3、3,4-(CH3)2、4-OCH3、4-CF3。
在式(I)中,所述各个基团具有如下所述的特别优选定义:
N’-苯基-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A1)、
N’-(2-氟苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A2)、
N’-(4-氟苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A3)、
N’-(2-氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A4)、
N’-(4-氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A5)、
N’-(2,4-二氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A6)、
N’-(2,4,6-三氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A7)、
N’-(4-溴苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A8)、
N’-(4-甲基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A9)、
N’-(4-甲氧基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A10)、
N’-(4-三氟甲基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A11)、
N’-(4-氟苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A12)、
N’-(2-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A13)、
N’-(3-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A14)、
N’-(4-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A15)、
N’-(4-溴苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A16)、
N’-(4-三氟甲基苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A17)、
N’-(4-氟苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A18)、
N’-(4-氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A19)、
N’-(2,4-二氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A20)、
N’-(2,4,6-三氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A21)、
N’-(4-溴苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A22)、
N’-(4-甲基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A23)、
N’-(4-甲氧基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A24)、
N’-(4-三氟甲基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A25)、
N’-苯基-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A26)、
N’-(2-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A27)、
N’-(4-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A28)、
N’-(2-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A29)、
N’-(3-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A30)、
N’-(4-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A31)、
N’-(2,4-二氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A32)、
N’-(2,4,6-三氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A33)、
N’-(4-溴苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A34)、
N’-(4-甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A35)、
N’-(3,4-二甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A36)、
N’-(4-甲氧基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A37)、
N’-(4-三氟甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A38)、
N’-苯基-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A39)、
N’-(4-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A40)、
N’-(4-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A41)、
N’-(4-溴苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A42)、
N’-(4-甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A43)。
本发明的第二个方面提供了制备式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物的方法,该方法以式(II)的化合物与取代苯肼(III)反应,制备式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物,其反应方程式可用下述通式(A)表示:
其中在上述各结构式中:
R1、R2、Y(n)均具有如前所述的相应基团的定义。
本发明的第三个方面涉及式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物在抑制植物病原真菌和防治植物真菌病害方面的应用,可应用于农药领域,作为杀菌剂。
本发明的式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物可以在植物保护中用于抑制下列植物病原真菌:小麦赤霉病菌、草莓灰霉病菌、水稻纹枯病菌、辣椒炭疽病菌。
本发明的式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物可以在植物保护中用于防治下列病原菌引起的作物真菌病害,但它不应视为是对本发明的任何限制:
防治麦类作物真菌病害:
镰孢属,如禾谷镰孢菌Fusarium graminearum,引起的小麦赤霉病;
丝核菌属,如禾谷丝核菌Rhizoctonia cereadis,引起的小麦纹枯病;
防治水稻作物真菌病害:
梨孢属,如灰梨孢菌Pyricularia grisea,引起的稻瘟病;
丝核菌属,如茄丝核菌Rhizoctonia solani,引起的水稻纹枯病;
防治水果作物真菌病害:
葡萄孢属,如灰葡萄孢菌Botrytis cinerea,引起的草莓灰霉病、葡萄灰霉病;
防治蔬菜作物真菌病害:
葡萄孢属,如灰葡萄孢菌Botrytis cinerea,引起的茄科蔬菜灰霉病,如辣椒灰霉病、茄子灰霉病;
炭疽菌属,如辣椒刺盘孢Colletotrichum capsici,引起的辣椒炭疽病。
本发明的化合物特别适合于用于防治麦类作物真菌病害,如小麦赤霉病;防治水稻作物真菌病害,如水稻纹枯病;防治水果作物真菌病害,如草莓灰霉病;防治蔬菜作物真菌病害,如辣椒炭疽病。
有益效果:
1、本发明专利所述的式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物的分子结构新颖,该结构式中含噻二嗪硫酮六元杂环、乙酰苯肼两种特征基团,六元杂环是饱和的1,3,5-噻二嗪-2-硫酮。
2、本发明专利所述的式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物的制备方法简便、原料易得、产率高。
3、本发明专利所述的式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物表现出显著的抑制植物病原真菌的活性,具有作为农药杀菌剂、防治植物真菌病害的用途,体现出本技术方案的应用价值。
具体实施方式
本发明的实质性特点可从下述实施例得以体现,但它不应视为是对本发明的任何限制。
制备实施例
实施例1:一种含噻二嗪硫酮的乙酰苯肼类化合物A1的制备
在常温条件下,在50mL单口瓶中加入30mL二氯甲烷、3mmol化合物(I-A1)和3.6mmol O-苯并三氮唑-N,N,N’,N’-四甲基脲四氟硼酸(TBTU),磁力搅拌,缓慢滴加6mmol三乙胺(TEA),滴完后,搅拌30min,加入3.75mmol苯肼(II-A1),继续搅拌反应,TLC监控反应进程,反应完成后抽滤,用二氯甲烷洗涤,烘干,选取合适的展开剂过柱提纯,得含噻二嗪硫酮的乙酰苯肼类化合物A1,其反应方程式如下:
采用实施例1的方法,依次制备了含噻二嗪硫酮的乙酰苯肼类化合物A2-A43,各化合物的名称、结构、物理参数及波谱数据如下:
N’-苯基-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A1)
白色粉末;收率70.2%;m.p.180.1-181.1℃;IR(KBr,cm-1)v:3273,2973,2886,1672,1601,1471,1459,1303,1236,1205,1119,832,759,630,624,562;1H NMR(400MHz,DMSO-d6)δ:9.93(d,J=2.7Hz,1H,CONH),7.77(d,J=2.7Hz,1H,ArNH),7.51-7.44(m,2H,ArH),7.37(t,J=7.4Hz,1H,ArH),7.28(d,J=7.3Hz,2H,ArH),7.09(t,J=7.8Hz,2H,ArH),6.71-6.63(m,3H,ArH),4.74(s,2H,NCH2N),4.70(s,2H,SCH2N),3.77(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.38,168.44,149.56,144.84,129.96,129.15,128.31,127.69,119.03,112.60,73.61,59.60,55.41,52.03;HRMS(MALDI)Calcd for C17H18N4NaOS2[M+Na]+:381.08143,found:381.08105.
N’-(2-氟苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A2)
白色粉末;收率71.1%;m.p.167.5-168.1℃;IR(KBr,cm-1)v:3674,3280,2977,2899,1673,1493,1469,1456,1303,1238,1204,1197,1119,1050,1016,769,757,733,695,675;1H NMR(400MHz,DMSO-d6)δ:9.98(d,J=1.8Hz,1H,CONH),7.70(s,1H,ArNH),7.48(t,J=7.6Hz,2H,ArH),7.37(t,J=7.4Hz,1H,ArH),7.28(d,J=7.3Hz,1H,ArH),7.10-7.02(m,1H,ArH),6.91(t,J=7.5Hz,1H,ArH),6.75-6.67(m,2H,ArH),4.75(s,2H,NCH2N),4.70(s,2H,SCH2N),3.78(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.35,168.57,151.76,149.38,144.81,137.15,137.04,129.96,128.31,127.71,124.90,119.26,119.19,115.41,115.23,113.98,113.91,73.64,59.54,52.06;HRMS(MALDI)Calcd for C17H17FN4NaOS2[M+Na]+:399.07200,found:399.07268.
N’-(4-氟苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A3)
白色粉末;收率61.8%;m.p.171.5-172.8℃;IR(KBr,cm-1)v:3255,3221,3074,2983,2924,1652,1502,1469,1449,1314,1209,1053,822,597,590,580,572,554,548;1HNMR(400MHz,DMSO-d6)δ:9.94(d,J=2.6Hz,1H,CONH),7.75(d,J=2.4Hz,1H,ArNH),7.48(t,J=7.6Hz,2H,ArH),7.37(t,J=7.4Hz,1H,ArH),7.27(d,J=7.3Hz,2H,ArH),6.93(t,J=8.8Hz,2H,ArH),6.73-6.62(m,2H,ArH),4.75(d,J=11.7Hz,2H,NCH2N),4.69(s,2H,SCH2N),3.76(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.40,168.52,157.48,155.16,146.12,144.84,129.98,128.33,127.68,127.48,115.71,115.49,113.89,113.81,73.65,59.61,52.08;HRMS(MALDI)Calcd for C17H17FN4NaOS2[M+Na]+:399.07200,found:399.07289.
N’-(2-氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A4)
白色粉末;收率47.1%;m.p.172.3-172.8℃;IR(KBr,cm-1)v:3299,3202,2971,2896,1656,1476,1460,1436,1322,1209,1106,1059,1019,746,710,692,668,652,632,625;1H NMR(400MHz,DMSO-d6)δ:10.07(s,1H,CONH),7.55-7.42(m,3H,ArNH+ArH),7.41-7.32(m,1H,ArH),7.28(d,J=7.9Hz,3H,ArH),7.08(t,J=7.7Hz,1H,ArH),6.77-6.67(m,2H,ArH),4.77(s,2H,NCH2N),4.70(s,2H,SCH2N),3.81(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.34,168.53,144.93,144.81,129.97,129.64,128.33,128.16,127.73,120.01,117.61,113.31,73.68,59.52,52.18;HRMS(MALDI)Calcd for C17H17ClN4NaOS2[M+Na]+:415.04245,found:415.04099.
N’-(4-氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A5)
白色粉末;收率68.5%;m.p.176.4-177.6℃;IR(KBr,cm-1)v:3202,2968,2889,1703,1660,1488,1456,1447,1435,1323,1242,1210,1115,1054,1019,821,762,697,619,610;1H NMR(400MHz,DMSO-d6)δ:9.98(s,1H,CONH),7.98(s,1H,ArNH),7.48(t,J=7.6Hz,2H,ArH),7.37(t,J=7.3Hz,1H,ArH),7.27(d,J=7.8Hz,2H,ArH),7.12(d,J=8.6Hz,2H,ArH),6.67(d,J=8.7Hz,2H,ArH),4.74(s,2H,NCH2N),4.69(s,2H,SCH2N),3.77(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.39,168.54,148.56,144.84,129.98,128.93,128.33,127.69,122.34,114.11,73.66,59.60,52.05;HRMS(MALDI)Calcd forC17H17ClN4NaOS2[M+Na]+:415.04245,found:415.04120.
N’-(2,4-二氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A6)
白色粉末;收率37.6%;m.p.173.6-174.6℃;IR(KBr,cm-1)v:3305,3199,2974,2899,1651,1587,1474,1462,1450,1317,1262,1208,1105,1057,1018,810,732,693,676,610,572;1H NMR(400MHz,DMSO-d6)δ:10.10(s,1H,CONH),7.70(s,1H,ArNH),7.48(t,J=7.6Hz,2H,ArH),7.42(d,J=2.0Hz,1H,ArH),7.37(t,J=7.4Hz,1H,ArH),7.27(d,J=7.8Hz,2H,ArH),7.13(dd,J=8.7,2.0Hz,1H,ArH),6.71(d,J=8.8Hz,1H,ArH),4.76(s,2H,NCH2N),4.70(s,2H,SCH2N),3.79(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.33,168.61,144.80,144.19,129.97,128.92,128.32,128.06,127.73,122.44,118.05,114.36,73.73,59.48,52.18;HRMS(MALDI)Calcd for C17H16Cl2N4NaOS2[M+Na]+:449.00348,found:449.00325.
N’-(2,4,6-三氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A7)
白色粉末;收率37.1%;m.p.168.1-168.6℃;IR(KBr,cm-1)v:3280,3224,2983,2896,1664,1565,1488,1469,1441,1324,1268,1228,1211,1126,1099,1072,1050,1016,882,607;1H NMR(400MHz,DMSO-d6)δ:10.13(d,J=1.4Hz,1H,CONH),7.48(s,2H,ArH),7.39-7.27(m,5H,ArH),7.20(d,J=1.3Hz,1H,ArNH),5.29(s,2H,COCH2),4.51(s,2H,NCH2N),4.46(s,2H,SCH2N);13C NMR(101MHz,DMSO-d6)δ:192.21,167.85,141.08,136.03,129.04,128.96,128.37,128.05,125.45,124.47,69.83,58.92,53.79,51.45;HRMS(MALDI)Calcdfor C17H16Cl3N4OS2[M+H]+:460.98256,found:460.98119.
N’-(4-溴苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A8)
白色粉末;收率77.2%;m.p.179.8-180.9℃;IR(KBr,cm-1)v:3204,2983,2899,1701,1656,1591,1485,1472,1456,1447,1434,1419,1323,1242,1114,1074,1018,1002,831,631;1H NMR(400MHz,DMSO-d6)δ:9.97(s,1H,CONH),7.98(s,1H,ArNH),7.48(t,J=7.6Hz,2H,ArH),7.37(t,J=7.4Hz,1H,ArH),7.31-7.19(m,4H),6.63(d,J=8.6Hz,2H,ArH),4.74(s,2H,NCH2N),4.69(s,2H,SCH2N),3.76(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.39,168.53,148.96,144.84,131.77,129.98,128.33,127.69,114.63,109.86,73.66,59.60,52.04;HRMS(MALDI)Calcd for C17H17BrN4NaOS2[M+Na]+:458.99194,found:458.99163.
N’-(4-甲基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A9)
白色粉末;收率71.2%;m.p.188.2-189.2℃;IR(KBr,cm-1)v:3208,2977,2896,1699,1659,1609,1587,1513,1488,1473,1447,1434,1321,1240,1209,1116,1055,1021,831,690,625;1H NMR(400MHz,DMSO-d6)δ:9.88(s,1H,CONH),7.59(s,1H,ArNH),7.47(t,J=7.5Hz,2H,ArH),7.37(t,1H,ArH),7.27(d,J=7.8Hz,2H,ArH),6.90(d,J=8.0Hz,2H,ArH),6.58(d,J=7.9Hz,2H,ArH),4.73(s,2H,NCH2N),4.69(s,2H,SCH2N),3.75(s,2H,COCH2),2.16(s,3H,ArCH3);13C NMR(101MHz,DMSO-d6)δ:193.72,168.37,146.96,144.85,129.97,129.58,128.27,127.70,112.86,73.61,59.62,52.06,20.66;HRMS(MALDI)Calcd forC18H20N4NaOS2[M+Na]+:395.09708,found:395.09952.
N’-(4-甲氧基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A10)
白色粉末;收率50.1%;m.p.153.6-154.9℃;IR(KBr,cm-1)v:3364,3280,2971,2896,1672,1596,1503,1469,1343,1317,1235,1210,1119,1013,962,799,692,610;1H NMR(400MHz,DMSO-d6)δ:9.91(s,1H,CONH),7.51-7.44(m,3H,ArNH+ArH),7.36(t,J=12.8,5.3Hz,1H,ArH),7.27(d,J=7.4Hz,2H,ArH),6.71(d,2H,ArH),6.63(d,J=8.9Hz,2H,ArH),4.73(s,2H,NCH2N),4.69(s,2H,SCH2N),3.74(s,2H,COCH2),3.64(s,3H,OCH3);13C NMR(101MHz,DMSO-d6)δ:193.37,168.36,153.11,144.83,143.41,129.95,128.30,127.68,114.63,114.11,73.60,59.58,55.72,55.40,52.06;HRMS(MALDI)Calcd for C18H21N4O2S2[M+H]+:389.11005,found:389.11337.
N’-(4-三氟甲基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A11)
白色粉末;收率65.3%;m.p.168.3-169.9℃;IR(KBr,cm-1)v:3246,3183,2977,2896,1655,1616,1521,1469,1312,1267,1211,1108,1056,1020,1010,836,757,668,610;1H NMR(400MHz,DMSO-d6)δ:10.09(s,1H,CONH),8.43(s,1H,ArNH),7.48(t,J=7.7Hz,2H,ArH),7.45-7.34(m,3H,ArH),7.28(d,J=7.5Hz,2H,ArH),6.78(d,J=8.5Hz,2H,ArH),4.76(s,2H,NCH2N),4.70(s,2H,SCH2N),3.80(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.40,168.63,152.71,144.84,129.96,129.40,128.31,127.70,126.61,126.57,111.94,73.70,59.54,52.03;HRMS(MALDI)Calcd for C18H17F3N4NaOS2[M+Na]+:449.06881,found:449.06818.
N’-(4-氟苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A12)
白色粉末;收率68.2%;m.p.176.4-177.8℃;IR(KBr,cm-1)v:3251,3220,3073,2985,2882,1654,1598,1505,1470,1407,1318,1238,1225,1208,1151,1105,1051,1019,843,825,659,618;1H NMR(400MHz,DMSO-d6)δ:9.96(s,1H,CONH),7.75(s,1H,ArNH),7.37-7.26(m,4H,ArH),6.94(t,J=8.8Hz,2H,ArH),6.72-6.63(m,2H,ArH),4.74(s,2H,NCH2N),4.68(s,2H,SCH2N),3.75(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:194.00,168.53,162.78,160.35,157.47,155.15,146.11,140.93,140.90,129.96,129.87,116.88,116.65,115.69,115.47,113.89,113.81,73.69,59.63,55.40,52.12;HRMS(MALDI)Calcd forC17H16F2N4NaOS2[M+Na]+:417.06258,found:417.06210.
N’-(2-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A13)
白色粉末;收率55.9%;m.p.167.8-168.9℃;IR(KBr,cm-1)v:3255,3173,2979,2873,1655,1595,1503,1478,1456,1322,1227,1106,1090,1058,1022,854,829,745,715,660,564;1H NMR(400MHz,DMSO-d6)δ:10.08(s,1H,CONH),7.46(s,1H,ArNH),7.33(s,2H,ArH),7.32(d,J=3.0Hz,2H,ArH),7.29-7.26(m,1H,ArH),7.09(t,J=8.1Hz,1H,ArH),6.77-6.70(m,2H,ArH),4.76(s,2H,NCH2N),4.70(s,2H,SCH2N),3.79(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.94,168.53,162.78,160.34,144.91,140.89,140.86,130.00,129.91,129.62,128.13,120.03,117.63,116.86,116.64,113.34,73.69,59.56,52.24;HRMS(MALDI)Calcd for C17H16ClFN4NaOS2[M+Na]+:433.03303,found:433.03524.
N’-(3-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A14)
白色粉末;收率65.5%;m.p.178.4-179.6℃;IR(KBr,cm-1)v:3292,2973,2898,1675,1593,1499,1479,1452,1351,1312,1218,1200,1117,1053,1023,852,827,790,780,685,661,638;1H NMR(400MHz,DMSO-d6)δ:10.01(s,1H,CONH),8.07(s,1H,ArNH),7.37-7.30(m,4H,ArH),7.11(t,J=8.0Hz,1H,ArH),6.74-6.66(m,2H,ArH),6.65-6.60(m,1H,ArH),4.75(s,2H,NCH2N),4.69(s,2H,SCH2N),3.78(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.96,168.59,162.79,160.35,151.15,140.92,140.89,133.97,130.80,129.94,129.85,118.49,116.89,116.66,111.86,111.25,73.70,59.61,55.39,52.10;HRMS(MALDI)Calcdfor C17H16ClFN4NaOS2[M+Na]+:433.03303,found:433.03501.
N’-(4-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A15)
白色粉末;收率62.9%;m.p.177.5-178.6℃;IR(KBr,cm-1)v:3216,2973,2885,1701,1659,1597,1501,1489,1452,1433,1423,1323,1314,1247,1219,1205,1112,1054,1022,855,713,640;1H NMR(400MHz,DMSO-d6)δ:9.99(s,1H,CONH),7.97(s,1H,ArNH),7.32(d,J=6.7Hz,4H,ArH),7.13(d,J=8.7Hz,2H,ArH),6.68(d,J=8.7Hz,2H,ArH),4.74(s,2H,NCH2N),4.68(s,2H,SCH2N),3.76(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:194.00,168.57,162.78,160.35,148.55,140.93,140.90,129.97,129.88,128.92,122.33,116.88,116.66,114.12,73.69,59.63,52.10;HRMS(MALDI)Calcd for C17H16ClFN4NaOS2[M+Na]+:433.03303,found:433.03587.
N’-(4-溴苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A16)
白色粉末;收率65.1%;m.p.179.1-180.3℃;IR(KBr,cm-1)v:3208,2935,2894,1698,1655,1589,1501,1486,1473,1453,1432,1423,1323,1247,1219,1112,1054,1022,855,713,669,641,613;1H NMR(400MHz,DMSO-d6)δ:9.99(d,J=2.1Hz,1H,CONH),7.99(d,J=1.7Hz,1H,ArNH),7.32(d,J=6.9Hz,4H,ArH),7.24(d,J=8.7Hz,2H,ArH),6.63(d,J=8.8Hz,2H,ArH),4.74(s,2H,NCH2N),4.68(s,2H,SCH2N),3.76(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.99,168.55,162.78,160.35,148.95,140.93,140.90,131.76,129.96,129.88,116.88,116.66,114.63,109.84,73.69,59.62,55.41,52.09;HRMS(MALDI)Calcd for C17H17BrFN4OS2[M+H]+:455.00057,found:454.99869.
N’-(4-三氟甲基苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A17)
白色粉末;收率66.7%;m.p.173.3-174.9℃;IR(KBr,cm-1)v:3208,2935,2894,1698,1655,1589,1501,1486,1473,1453,1432,1423,1323,1247,1219,1112,1054,1022,855,713,669,641,613;1H NMR(400MHz,DMSO-d6)δ:10.09(s,1H,CONH),8.42(s,1H,ArNH),7.42(d,J=8.6Hz,2H,ArH),7.37-7.31(m,4H,ArH),6.78(d,J=8.5Hz,2H,ArH),4.76(s,2H,NCH2N),4.69(s,2H,SCH2N),3.79(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:194.01,168.63,162.78,160.34,152.69,140.93,140.90,129.96,129.87,126.78,126.62,126.61,126.58,126.54,126.50,124.10,118.91,118.59,116.86,116.63,111.95,73.72,59.60,52.10;HRMS(MALDI)Calcd for C18H17F4N4OS2[M+H]+:445.07744,found:445.07772.
N’-(4-氟苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A18)
白色粉末;收率74.2%;m.p.172.4-173.9℃;IR(KBr,cm-1)v:3358,3265,2987,1675,1488,1451,1430,1349,1323,1248,1228,1166,1123,1078,1032,985,934,930,825,737,677,570;1H NMR(400MHz,DMSO-d6)δ:9.82(d,J=1.8Hz,1H,CONH),7.64(s,1H,ArNH),7.40-7.30(m,5H,ArH),6.95(t,J=8.8Hz,2H,ArH),6.65-6.58(m,2H,ArH),5.30(s,2H,ArCH2),4.57(s,2H,NCH2N),4.49(s,2H,SCH2N),3.42(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:192.35,168.43,157.45,155.13,146.08,146.06,136.02,129.12,128.27,128.12,115.69,115.47,113.87,113.79,69.99,59.01,53.77,52.18;HRMS(MALDI)Calcd forC18H19FN4NaOS2[M+Na]+:413.08765,found:413.08802.
N’-(4-氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A19)
白色粉末;收率74.2%;m.p.172.4-173.9℃;IR(KBr,cm-1)v:3359,3277,2988,2904,1674,1583,1496,1487,1463,1433,1351,1314,1224,1117,1079,952,942,927,807,759,643,604;1H NMR(400MHz,DMSO-d6)δ:9.85(s,1H,CONH),7.87(d,J=1.8Hz,1H,ArNH),7.43-7.35(m,4H,ArH),7.35-7.29(m,1H,ArH),7.14(d,J=8.7Hz,2H,ArH),6.63(d,J=8.7Hz,2H,ArH),5.31(s,2H,ArCH2),4.58(s,2H,NCH2N),4.49(s,2H,SCH2N),3.43(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:192.34,168.45,148.51,136.02,129.12,128.92,128.26,128.11,122.27,114.10,69.99,58.99,53.77,52.15;HRMS(MALDI)Calcd forC18H19ClN4NaOS2[M+Na]+:429.05810,found:429.05780.
N’-(2,4-二氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A20)
白色粉末;收率31.1%;m.p.147.6-148.8℃;IR(KBr,cm-1)v:3308,3220,2985,2898,1675,1586,1536,1477,1431,1352,1323,1220,1163,1105,1079,985,804,737,700,631,543;1H NMR(400MHz,DMSO-d6)δ:9.99(s,1H,CONH),7.53(s,1H,ArNH),7.41(d,J=2.3Hz,1H,ArH),7.38(d,J=4.3Hz,3H,ArH),7.35-7.31(m,1H,ArH),7.16(dd,J=8.7,2.3Hz,1H,ArH),5.31(s,2H,ArCH2),4.58(s,2H,NCH2N),4.50(s,2H,SCH2N),3.45(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:192.28,168.51,144.12,136.07,129.12,128.86,128.31,128.12,122.45,118.02,114.40,69.92,58.94,53.80,52.18;HRMS(MALDI)Calcdfor C18H18Cl2N4NaOS2[M+Na]+:463.01913,found:463.01624.
N’-(2,4,6-三氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A21)
白色粉末;收率56.3%;m.p.177.3-178.8℃;IR(KBr,cm-1)v:3330,3198,2992,2904,1680,1535,1482,1450,1330,1315,1229,1129,1101,1072,981,966,923,872,805,696,614;1H NMR(400MHz,DMSO-d6)δ:10.24(d,J=1.8Hz,1H,CONH),7.50(s,2H,ArH),7.49-7.42(m,2H,ArH+ArNH),7.39-7.33(m,2H,ArH),7.24-7.19(m,2H,ArH),4.71(s,2H,NCH2N),4.65(s,2H,SCH2N),3.68(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:193.24,168.09,144.67,141.13,129.92,128.94,128.29,127.67,125.53,124.60,73.70,59.40,51.49;HRMS(MALDI)Calcd for C18H17Cl3N4NaOS2[M+Na]+:496.98016,found:496.97720.
N’-(4-溴苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A22)
白色粉末;收率88.1%;m.p.172.1-173.6℃;IR(KBr,cm-1)v:3358,3270,2985,2898,1674,1496,1484,1463,1454,1431,1352,1315,1226,1166,1117,1079,1068,874,698,642,602,550;1H NMR(400MHz,DMSO-d6)δ:9.84(d,J=2.4Hz,1H,CONH),7.88(d,J=2.3Hz,1H,ArNH),7.42-7.35(m,4H,ArH),7.34-7.29(m,1H,ArH),7.28-7.19(m,3H,ArH),6.58(d,J=8.8Hz,2H,ArH),5.30(s,2H,ArCH2),4.57(s,2H,NCH2N),4.49(s,2H,SCH2N),3.43(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:192.34,168.44,148.92,136.02,131.75,129.12,128.26,128.11,114.61,109.78,70.00,58.99,53.77,52.15;HRMS(MALDI)Calcdfor C18H20BrN4OS2[M+H]+:451.02564,found:451.02436.
N’-(4-甲基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A23)
白色粉末;收率66.9%;m.p.189.2-190.5℃;IR(KBr,cm-1)v:3358,3273,2985,2894,1674,1605,1508,1496,1465,1453,1431,1351,1316,1228,1117,1078,984,944,875,725,667,629;1H NMR(400MHz,DMSO-d6)δ:9.76(d,J=3.0Hz,1H,CONH),7.49(d,J=3.0Hz,1H,ArNH),7.39-7.26(m,5H,ArH),6.92(d,J=8.2Hz,2H,ArH),6.54(d,J=8.4Hz,2H,ArH),5.30(s,2H,ArCH2),4.56(s,2H,NCH2N),4.49(s,2H,SCH2N),3.41(s,2H,COCH2),2.17(s,3H,ArCH3);13C NMR(101MHz,DMSO-d6)δ:192.35,168.29,147.25,136.02,129.56,129.11,128.27,128.10,127.65,112.88,70.01,59.00,53.82,52.18,20.65;HRMS(MALDI)Calcdfor C19H22N4NaOS2[M+Na]+:409.11273,found:409.11420.
N’-(4-甲氧基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A24)
白色粉末;收率76.3%;m.p.177.6-178.9℃;IR(KBr,cm-1)v:3358,3270,2982,2894,1675,1611,1496,1454,1317,1230,1166,1113,1079,1064,1029,982,938,874,835,699;1H NMR(400MHz,DMSO-d6)δ:9.77(d,J=2.6Hz,1H,CONH),7.40-7.33(m,5H,ArH+ArNH),7.32-7.26(m,1H,ArH),6.73(d,J=8.8Hz,2H,ArH),6.60(d,J=8.7Hz,2H,ArH),5.30(s,2H,ArCH2),4.56(s,2H,NCH2N),4.49(s,2H,SCH2N),3.65(s,3H,CH3),3.40(s,2H,COCH2);13CNMR(101MHz,DMSO-d6)δ:192.35,168.28,153.11,143.38,136.02,129.11,128.26,128.11,114.64,114.12,70.00,58.99,55.78,55.72,53.80,52.19;HRMS(MALDI)Calcd forC19H22N4NaO2S2[M+Na]+:425.10764,found:425.10567.
N’-(4-三氟甲基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A25)
白色粉末;收率72.6%;m.p.163.7-164.8℃;IR(KBr,cm-1)v:3355,3264,2985,2894,1673,1472,1454,1353,1315,1230,1166,1113,1033,866,828,799,672,633,599;1HNMR(400MHz,DMSO-d6)δ:9.96(s,1H,CONH),8.32(s,1H,ArNH),7.43(d,J=8.6Hz,2H,ArH),7.40-7.16(m,5H,ArH),6.73(d,J=8.5Hz,2H,ArH),5.31(s,2H,ArCH2),4.58(s,2H,NCH2N),4.50(s,2H,SCH2N),3.46(s,2H,COCH2);13C NMR(101MHz,DMSO-d6)δ:192.35,168.53,152.67,136.03,129.11,128.26,128.10,126.60,126.56,124.13,118.84,118.52,111.93,70.01,58.98,55.39,53.77,52.15;HRMS(MALDI)Calcd for C19H20F3N4OS2[M+H]+:441.10252,found:441.10353.
N’-苯基-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A26)
白色粉末;收率64.5%;m.p.176.2-177.5℃;IR(KBr,cm-1)v:3360,3280,3032,2979,2907,1672,1597,1511,1494,1473,1362,1351,1323,1099,976,949,890,879,756,730,690,660,610;1H NMR(400MHz,DMSO-d6)δ:9.89(s,1H,CONH),7.75(d,J=2.5Hz,1H,ArNH),7.14(t,J=7.7Hz,2H,ArH),6.74-6.67(m,3H,ArH),4.55(s,4H,NCH2N+SCH2N),3.56(s,2H,COCH2),3.39(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.57,168.61,149.59,129.20,119.06,112.64,71.89,58.90,52.27,40.41;HRMS(MALDI)Calcd for C12H16N4NaOS2[M+Na]+:319.06578,found:319.06563.
N’-(2-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A27)
白色粉末;收率73.1%;m.p.165.0-166.5℃;IR(KBr,cm-1)v:3362,3280,3070,2979,1675,1617,1511,1486,1470,1450,1363,1351,1320,1241,1193,1100,1089,978,949,923,888,876,745,624;1H NMR(400MHz,DMSO-d6)δ:9.95(s,1H,CONH),7.66(s,1H,ArNH),7.11-7.03(m,1H,ArH),6.99(t,J=7.7Hz,1H,ArH),6.82-6.69(m,2H,ArH),4.54(s,4H,NCH2N+SCH2N),3.57(s,2H,COCH2),3.39(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.54,168.72,151.78,149.41,137.19,137.08,125.02,119.27,119.20,115.41,115.23,114.07,99.99,71.82,58.87,52.26;HRMS(MALDI)Calcd for C12H16FN4OS2[M+H]+:315.07441,found:315.07138.
N’-(4-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A28)
白色粉末;收率85.6%;m.p.165.8-166.7℃;IR(KBr,cm-1)v:3366,3282,3054,2976,2932,2907,1673,1502,1465,1350,1322,1198,1100,1091,945,891,831,807,687,652,557;1H NMR(400MHz,DMSO-d6)δ:9.91(s,1H,CONH),7.73(d,J=2.8Hz,1H,ArNH),7.02-6.94(m,2H,ArH),6.76-6.68(m,2H,ArH),4.53(s,4H,NCH2N+SCH2N),3.55(s,2H,COCH2),3.39(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.57,168.66,157.47,155.16,146.15,115.73,115.51,113.90,113.82,71.90,58.90,52.29;HRMS(MALDI)Calcd for C12H16FN4OS2[M+H]+:315.07441,found:315.07436.
N’-(2-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A29)
白色粉末;收率80.3%;m.p.170.1-171.4℃;IR(KBr,cm-1)v:3280,2992,2901,1667,1592,1514,1475,1341,1313,1198,1103,957,893,779,747,710,679,655,628,603;1H NMR(400MHz,DMSO-d6)δ:10.04(s,1H,CONH),7.44(s,1H,ArNH),7.29(d,J=7.8Hz,1H,ArH),7.16(t,J=7.7Hz,1H,ArH),6.82-6.72(m,2H,ArH),4.55(s,4H,NCH2N+SCH2N),3.59(s,2H,COCH2),3.39(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.51,168.65,144.94,129.61,128.23,120.05,117.64,113.40,71.80,58.89,52.35,40.44;HRMS(MALDI)Calcdfor C12H16ClN4OS2[M+H]+:331.04486,found:331.04512.
N’-(3-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A30)
白色粉末;收率75.5%;m.p.161.1-162.4℃;IR(KBr,cm-1)v:3372,3268,2982,2910,1681,1601,1510,1475,1395,1353,1323,1266,1231,1199,1100,1071,1011,991,977,955,925,874,726,685;1H NMR(400MHz,DMSO-d6)δ:9.95(s,1H,CONH),8.06(s,1H,ArNH),7.15(t,J=8.0Hz,1H,ArH),6.76-6.62(m,3H,ArH),4.54(s,4H,NCH2N+SCH2N),3.58(s,2H,COCH2),3.38(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.55,168.73,151.18,133.98,130.86,118.49,111.88,111.28,71.88,58.90,52.23,40.42;HRMS(MALDI)Calcdfor C12H16ClN4OS2[M+H]+:331.04486,found:331.04504.
N’-(4-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A31)
白色粉末;收率65.4%;m.p.166.3-167.6℃;IR(KBr,cm-1)v:3366,3278,2976,2904,1673,1592,1509,1487,1464,1350,1321,1240,1199,1094,1004,978,952,893,836,811,702,650,549;1H NMR(400MHz,DMSO-d6)δ:9.93(d,J=2.4Hz,1H,CONH),7.94(d,J=2.2Hz,1H,ArNH),7.17(d,J=8.8Hz,2H,ArH),6.71(d,J=8.8Hz,2H,ArH),4.53(s,4H,NCH2N+SCH2N),3.56(s,2H,COCH2),3.38(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.56,168.69,148.55,128.96,122.34,114.14,71.90,58.92,52.29,40.42;HRMS(MALDI)Calcdfor C12H16ClN4OS2[M+H]+:331.04486,found:331.04368.
N’-(2,4-二氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A32)
白色粉末;收率93.2%;m.p.168.2-169.1℃;IR(KBr,cm-1)v:3278,2987,2898,1678,1575,1517,1476,1417,1393,1352,1328,1269,1197,1152,1101,1044,1010,928,891,863,803729,686,575;1H NMR(400MHz,DMSO-d6)δ:10.07(s,1H,CONH),7.65(s,1H,ArNH),7.43(d,J=2.1Hz,1H,ArH),7.22(dd,J=8.8,2.2Hz,1H,ArH),6.77(d,J=8.8Hz,1H,ArH),4.54(s,4H,NCH2N+SCH2N),3.58(s,2H,COCH2),3.40(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.49,168.73,144.20,128.89,128.17,122.44,118.03,114.44,71.79,58.85,55.40,52.31,40.42;HRMS(MALDI)Calcd for C12H14Cl2N4NaOS2[M+Na]+:386.98783,found:386.99390.
N’-(2,4,6-三氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A33)
白色粉末;收率52.9%;m.p.159.5-160.8℃;IR(KBr,cm-1)v:3358,3333,3264,2970,2901,1662,1567,1505,1478,1444,1324,1314,1200,1098,1011,924,876,861,771,717,675,651,576;1H NMR(400MHz,DMSO-d6)δ:10.18(d,J=1.9Hz,1H,CONH),7.50(s,2H,ArH),7.36(d,J=1.8Hz,1H,ArNH),4.49(d,J=3.1Hz,4H,NCH2N+SCH2N),3.48(s,2H,COCH2),3.35(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.41,168.09,141.16,128.97,125.39,124.43,71.74,58.77,55.40,51.57,40.36;HRMS(MALDI)Calcd forC12H13Cl3N4NaOS2[M+Na]+:420.94886,found:420.94864.
N’-(4-溴苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A34)
白色粉末;收率74.3%;m.p.161.9-162.8℃;IR(KBr,cm-1)v:3360,3271,2970,2907,1671,1583,1510,1483,1464,1349,1315,1201,1097,1068,953,931,894,820,806,698,649,550;1H NMR(400MHz,DMSO-d6)δ:9.94(s,1H,CONH),7.96(d,J=1.9Hz,1H,ArNH),7.29(d,J=8.6Hz,2H,ArH),6.67(d,J=8.7Hz,2H,ArH),4.53(s,4H,NCH2N+SCH2N),3.56(s,2H,COCH2),3.38(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.55,168.68,148.95,131.80,114.65,109.86,71.90,58.92,52.28,40.43;HRMS(MALDI)Calcd for C12H15BrN4NaOS2[M+Na]+:396.97629,found:396.97978.
N’-(4-甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A35)
白色粉末;收率90.5%;m.p.164.1-165.4℃;IR(KBr,cm-1)v:3361,3274,2970,2901,1672,1611,1576,1508,1464,1350,1318,1237,1119,1097,1068,978,953,929,891,812,720,607,577;1H NMR(400MHz,DMSO-d6)δ:9.85(d,J=2.2Hz,1H,CONH),7.57(d,J=2.6Hz,1H,ArNH),6.95(d,J=8.1Hz,2H,ArH),6.62(d,J=8.1Hz,2H,ArH),4.53(s,4H,NCH2N+SCH2N),3.54(s,2H,COCH2),3.38(s,3H,NCH3),2.17(s,3H,ArCH3);13C NMR(101MHz,DMSO-d6)δ:190.57,168.52,147.30,129.60,127.70,112.90,71.86,58.91,52.27,40.41,20.65;HRMS(MALDI)Calcd for C13H18N4NaOS2[M+Na]+:333.08143,found:333.08124.
N’-(3,4-二甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A36)
白色粉末;收率58.2%;m.p.176.5-177.6℃;IR(KBr,cm-1)v:3361,3342,3285,2970,2901,1671,1612,1512,1471,1447,1399,1368,1350,1317,1237,1200,1101,979,931,854,818,668,628,590;1H NMR(400MHz,DMSO-d6)δ:9.83(d,J=3.0Hz,1H,CONH),7.48(d,J=3.0Hz,1H,ArNH),6.89(d,J=8.1Hz,1H,ArH),6.52(s,1H,ArH),6.45(d,J=8.0Hz,1H,ArH),4.53(s,4H,NCH2N+SCH2N),3.54(s,2H,COCH2),3.38(s,3H,NCH3),2.12(s,3H,ArCH3),2.09(s,3H,ArCH3);13C NMR(101MHz,DMSO-d6)δ:190.56,168.48,147.64,136.64,130.13,126.52,114.31,110.31,71.83,58.86,52.21,20.21,18.97;HRMS(MALDI)Calcdfor C14H20N4NaOS2[M+Na]+:347.09708,found:347.09680.
N’-(4-甲氧基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A37)
白色粉末;收率57.1%;m.p.167.3-168.4℃;IR(KBr,cm-1)v:3357,3272,2973,2898,1671,1505,1475,1351,1320,1237,1198,1096,1032,952,891,826,801,728,715,666,637,621;1H NMR(400MHz,DMSO-d6)δ:9.86(d,J=3.3Hz,1H,CONH),7.42(d,J=3.4Hz,1H,ArNH),6.76(d,J=8.9Hz,2H,ArH),6.68(d,J=8.9Hz,2H,ArH),4.53(s,4H,NCH2N+SCH2N),3.66(s,3H,OCH3),3.53(s,2H,COCH2),3.38(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.56,168.51,153.14,143.44,114.67,114.15,71.87,58.89,55.73,52.29,40.40;HRMS(MALDI)Calcd for C13H19N4O2S2[M+H]+:327.09440,found:327.09398.
N’-(4-三氟甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼(A38)
白色粉末;收率53.6%;m.p.177.2-178.6℃;IR(KBr,cm-1)v:3352,3269,2987,2901,1671,1614,1515,1477,1401,1368,1348,1317,1267,1232,1201,1180,1158,1099,1058,1007,979,952,639;1H NMR(400MHz,DMSO-d6)δ:10.05(s,1H,CONH),8.40(s,1H,ArNH),7.47(d,J=8.6Hz,2H,ArH),6.81(d,J=8.5Hz,2H,ArH),4.55(s,4H,NCH2N+SCH2N),3.59(s,2H,COCH2),3.39(s,3H,NCH3);13C NMR(101MHz,DMSO-d6)δ:190.56,168.78,152.72,126.82,126.65,126.62,124.13,118.87,118.56,111.95,71.91,58.89,52.26,40.41;HRMS(MALDI)Calcd for C13H16F3N4OS2[M+H]+:365.07122,found:365.07071.
N’-苯基-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A39)
白色粉末;收率47.6%;m.p.151.2-152.6℃;IR(KBr,cm-1)v:3245,3223,2985,2970,2891,1659,1505,1330,1319,1306,1205,1097,1081,943,923,892,832,734,695,563,551;1H NMR(400MHz,DMSO-d6)δ:10.04(s,1H,CONH),7.75(s,1H,ArNH),7.14(t,J=7.6Hz,2H,ArH),6.73-6.68(m,3H,ArH),4.71-4.61(m,2H,NCH2N),4.51-4.41(m,2H,SCH2N),3.68(q,J=6.6Hz,1H,CH3CH),3.39(s,3H,NCH3),1.34(d,J=6.7Hz,3H,CH3CH);13C NMR(101MHz,DMSO-d6)δ:191.15,172.00,149.70,129.26,119.12,119.04,112.60,69.00,56.81,56.18,40.33,16.86;HRMS(MALDI)Calcd for C13H18N4NaOS2[M+Na]+:333.08143,found:333.08195.
N’-(4-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A40)
白色粉末;收率45.9%;m.p.184.3-185.6℃;IR(KBr,cm-1)v:3327,3198,2976,2901,1678,1595,1537,1483,1451,1329,1317,1230,1130,1100,1078,982,964,923,872,804,698,668,652,631;1H NMR(400MHz,DMSO-d6)δ:10.05(d,J=3.1Hz,1H,CONH),7.74(d,J=3.1Hz,1H,ArNH),7.03-6.95(m,2H,ArH),6.73-6.66(m,2H,ArH),4.70-4.60(m,2H,NCH2N),4.49-4.41(m,2H,SCH2N),3.66(q,J=6.7Hz,1H,CH3CH),3.38(s,3H,NCH3),1.33(d,J=6.8Hz,3H,CH3CH);13C NMR(101MHz,DMSO-d6)δ:191.14,172.02,157.50,155.18,146.25,146.24,115.82,115.60,113.85,113.77,68.97,56.82,56.20,40.32,16.81;HRMS(MALDI)Calcd for C13H17FN4NaOS2[M+Na]+:351.07200,found:351.07234.
N’-(4-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A41)
白色粉末;收率94.5%;m.p.186.5-187.8℃;IR(KBr,cm-1)v:3204,2966,2898,1658,1586,1484,1345,1328,1317,1210,1097,1078,960,944,922,891,825,803,700,621;1H NMR(400MHz,DMSO-d6)δ:10.08(d,J=2.7Hz,1H,CONH),7.95(d,J=2.6Hz,1H,ArNH),7.18(d,J=8.8Hz,2H,ArH),6.69(d,J=8.8Hz,2H,ArH),4.71-4.60(m,2H,NCH2N),4.50-4.41(m,2H,SCH2N),3.67(q,J=6.7Hz,1H,CH3CH),3.39(s,3H,NCH3),1.33(d,J=6.8Hz,3H,CH3CH);13C NMR(101MHz,DMSO-d6)δ:191.14,172.06,148.68,129.05,122.39,114.09,68.97,56.84,56.23,40.32,16.81;HRMS(MALDI)Calcd for C13H17ClN4NaOS2[M+Na]+:367.04245,found:367.04197.
N’-(4-溴苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A42)
白色粉末;收率94.5%;m.p.186.5-187.8℃;IR(KBr,cm-1)v:3246,2987,2907,1655,1512,1483,1453,1354,1329,1320,1308,1274,1241,1208,1134,1099,1085,1006,959,942,924,889,730,668,564;1H NMR(400MHz,DMSO-d6)δ:10.08(d,J=2.7Hz,1H,CONH),7.97(d,J=2.6Hz,1H,ArNH),7.30(d,J=8.8Hz,2H,ArH),6.65(d,J=8.9Hz,2H,ArH),4.71-4.59(m,2H,NCH2N),4.50-4.41(m,2H,SCH2N),3.67(q,J=6.8Hz,1H,CH3CH),3.39(s,3H,NCH3),1.33(d,J=6.8Hz,3H,CH3CH);13C NMR(101MHz,DMSO-d6)δ:191.14,172.05,149.08,131.89,114.60,109.90,68.97,56.83,56.22,40.33,16.82;HRMS(MALDI)Calcdfor C13H17BrN4NaOS2[M+Na]+:410.99194,found:410.99170.
N’-(4-甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼(A43)
白色粉末;收率94.5%;m.p.186.5-187.8℃;IR(KBr,cm-1)v:3280,3239,2976,2879,1690,1660,1600,1519,1493,1454,1329,1318,1307,1207,1099,1082,960,941,924,891,787,756,743,689,575;1H NMR(400MHz,DMSO-d6)δ:10.00(d,J=3.2Hz,1H,CONH),7.57(d,J=3.2Hz,1H,ArNH),6.95(d,J=8.2Hz,2H,ArH),6.61(d,J=8.4Hz,2H,ArH),4.70-4.60(m,2H,NCH2N),4.49-4.40(m,2H,SCH2N),3.66(q,J=6.7Hz,1H,CH3CH),3.38(s,3H,NCH3),2.17(s,3H,ArCH3),1.32(d,J=6.8Hz,3H,CH3CH);13C NMR(101MHz,DMSO-d6)δ:191.14,171.90,147.45,129.66,127.74,112.85,69.00,56.77,56.12,40.32,20.63,16.85;HRMS(MALDI)Calcd for C14H20N4NaOS2[M+Na]+:347.09708,found:347.09692.
用途实施例
实施例2:本发明式(I)的一种含噻二嗪硫酮基团的乙酰苯肼类化合物A1-A43的杀
菌活性
采用菌丝生长速率法(具体测定方法的参考文献:Chem.Res.Chin.Univ.2015,31(2):228-234.)测定了一种含噻二嗪硫酮基团的乙酰苯肼类化合物(I)中的A1-A43化合物对四种供试植物病原真菌小麦赤霉病菌(Fusarium graminearum)、草莓灰霉病菌(Botrytis cinerea)、水稻纹枯病菌(Rhizoctonia solani)和辣椒炭疽病菌(Colletotrichum capsici)的杀菌活性,以多菌灵、嘧菌酯、吡噻菌胺作为对照药剂。EC50测定结果列于表1。
表1显示,含噻二嗪硫酮基团的乙酰苯肼类化合物A1-A43对四种供试植物病原菌小麦赤霉病菌、蔬菜灰霉病菌、水稻纹枯病菌和辣椒炭疽病菌具有显著的杀菌活性。化合物A5、A12、A15、A16、A18、A19、A22、A28、A40、A41对小麦赤霉病菌的EC50值小于3μg/mL,其中化合物A12、A15、A16、A40的EC50值小于2μg/mL。化合物A3、A5、A8、A12、A15、A16、A19、A28、A31、A34、A40、A41对草莓灰霉病菌的EC50值小于2μg/mL,其中化合物A5和A8对草莓灰霉病菌的EC50值小于1μg/mL,分别为0.8503μg/mL和0.6599μg/mL,接近甚至优于对照药剂吡噻菌胺的0.8241μg/mL。化合物A3、A5、A8、A11、A12-A20、A22、A25、A27、A28、A30-A32、A34、A38、A40-A42对水稻纹枯病菌的EC50值小于1μg/mL,其中化合物A5、A8、A15-A17、A25、A31、A32、A34、A41的EC50值小于对照药剂多菌灵的0.5474μg/mL。化合物A7、A17、A20、A21、A25、A27、A29、A32、A33、A38对辣椒炭疽病菌的EC50值小于2μg/mL,其中化合物A7、A25、A33、A38小于1μg/mL。
表1 含噻二嗪硫酮基团的乙酰苯肼类化合物A1-A43对4种植物病原真菌的EC50值(μg/mL)
Claims (8)
2.根据权利要求1所述的一种含噻二嗪硫酮基团的乙酰苯肼类化合物,其特征在于:
R1选自C1-6烷基、苯基、取代苯基、苄基,所述的取代基团选自1-3个卤素;
R2选自H、C1-6烷基;
Y(n)中,n=1-3取代,Y(n)选自下列1-3个基团:H、F、Cl、Br、C1-6烷基、OC1-6烷基、1-5个卤素取代的C1-6烷基。
3.根据权利要求2所述的一种含噻二嗪硫酮基团的乙酰苯肼类化合物,其特征在于:
R1选自CH3、苯基、4-氟苯基、苄基;
R2选自H、CH3;
Y(n)选自H、2-F、4-F、2-Cl、3-Cl、4-Cl、4-Br、2,4-(Cl)2、2,4,6-(Cl)3、4-CH3、3,4-(CH3)2、4-OCH3、4-CF3。
4.根据权利要求3所述的一种含噻二嗪硫酮基团的乙酰苯肼类化合物,其特征在于其为如下所述化合物之一:
N’-苯基-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2-氟苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氟苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2-氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2,4-二氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2,4,6-三氯苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-溴苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-甲基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-甲氧基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-三氟甲基苯基)-2-(5-苯基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氟苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(3-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氯苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-溴苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-三氟甲基苯基)-2-(5-(4-氟苯基)-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氟苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2,4-二氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2,4,6-三氯苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-溴苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-甲基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-甲氧基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-三氟甲基苯基)-2-(5-苯甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-苯基-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(3-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2,4-二氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(2,4,6-三氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-溴苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(3,4-二甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-甲氧基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-(4-三氟甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)乙酰肼、
N’-苯基-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼、
N’-(4-氟苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼、
N’-(4-氯苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼、
N’-(4-溴苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼、
N’-(4-甲基苯基)-2-(5-甲基-6-硫-1,3,5-噻二嗪-3-基)丙酰肼。
5.权利要求1-4中任一项所述的一种含噻二嗪硫酮基团的乙酰苯肼类化合物在抑制植物病原真菌方面的应用。
6.根据权利要求5所述的应用,其特征在于权利要求1-4中任一项所述的一种含噻二嗪硫酮基团的乙酰苯肼类化合物在抑制小麦赤霉病菌、草莓灰霉病菌、水稻纹枯病菌、辣椒炭疽病菌方面的应用。
7.权利要求1-4中任一项所述的一种含噻二嗪硫酮基团的乙酰苯肼类化合物在防治植物真菌病害方面的应用。
8.根据权利要求7所述的应用,其特征在于权利要求1-4中任一项所述的一种含噻二嗪硫酮基团的乙酰苯肼类化合物在防治小麦赤霉病、草莓灰霉病、水稻纹枯病、辣椒炭疽病方面的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810830434.2A CN110746375B (zh) | 2018-07-23 | 2018-07-23 | 一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810830434.2A CN110746375B (zh) | 2018-07-23 | 2018-07-23 | 一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110746375A CN110746375A (zh) | 2020-02-04 |
CN110746375B true CN110746375B (zh) | 2022-11-29 |
Family
ID=69275611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810830434.2A Active CN110746375B (zh) | 2018-07-23 | 2018-07-23 | 一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110746375B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2863864A (en) * | 1958-12-09 | Chchjconh- | ||
US4029652A (en) * | 1976-03-10 | 1977-06-14 | American Cyanamid Company | Tetrahydro-3-(4-pyridylmethyl)-2H-1,3,5-thiadiazine-2-thione |
DE2846127A1 (de) * | 1978-10-23 | 1980-04-30 | Basf Ag | 1,2,4-triazol-1-yl-verbindungen, ihre hersttellung und verwendung als fungizide |
CN1098713A (zh) * | 1992-11-12 | 1995-02-15 | Basf公司 | 取代的邻乙烯基苯乙酸衍生物 |
-
2018
- 2018-07-23 CN CN201810830434.2A patent/CN110746375B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2863864A (en) * | 1958-12-09 | Chchjconh- | ||
US4029652A (en) * | 1976-03-10 | 1977-06-14 | American Cyanamid Company | Tetrahydro-3-(4-pyridylmethyl)-2H-1,3,5-thiadiazine-2-thione |
DE2846127A1 (de) * | 1978-10-23 | 1980-04-30 | Basf Ag | 1,2,4-triazol-1-yl-verbindungen, ihre hersttellung und verwendung als fungizide |
CN1098713A (zh) * | 1992-11-12 | 1995-02-15 | Basf公司 | 取代的邻乙烯基苯乙酸衍生物 |
Non-Patent Citations (1)
Title |
---|
New 2H-Tetrahydro-1,3,5-thiadiazine-2-thiones Incorporating Glycine and Glycinamide as Potential Antifungal Agents;Tarek Aboul-Fadl 等;《Arch. Pharm. Pharm. Med. Chem.》;20021231;438–442 * |
Also Published As
Publication number | Publication date |
---|---|
CN110746375A (zh) | 2020-02-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW304938B (zh) | ||
US5166165A (en) | Fungicidal agents based on heterocyclically substituted sulphones | |
UA59380C2 (uk) | Галогенпіримідиніларил(тіо)етери, засіб та спосіб боротьби з шкідниками, проміжні сполуки | |
HU226907B1 (en) | Tetrazoyl oxime derivatives and fungicidal compositions containing thereof | |
JP2006290883A (ja) | 置換ヘテロ環カルボン酸アニリド誘導体、その中間体及び農園芸用薬剤並びにその使用方法 | |
JP2002506060A (ja) | ヘテロアリール置換ベンジルフェニルエーテル、その製造方法、並びに有害菌類及び有害動物防除用としての使用法 | |
CN101715446A (zh) | 制备酰胺化合物的方法 | |
US4782086A (en) | E-isomers of N.sup.α -(2-cyano-2-alkoximinoacetyl)-amino acid derivatives, compositions and fungicidal use | |
CA1164871A (en) | Isoxazolylbenzamides | |
US5104886A (en) | Amide derivatives, processes for production thereof, and agricultural-horticultural fungicide containing them | |
DE19900571A1 (de) | Phenyltetrazolinone | |
JP2818222B2 (ja) | 複素環式置換α―アリール―アクリル酸メチルエステル、ならびに該化合物を含有する殺菌剤および殺虫剤 | |
CN110746375B (zh) | 一种含噻二嗪硫酮基团的乙酰苯肼类化合物、制备方法及应用 | |
CN110746363B (zh) | 一种含酰肼的喹唑啉酮类衍生物、制备方法及应用 | |
NZ311679A (en) | Triazoline or isoxazoline phenyl bis-oxime derivatives, certain phenyl bis-oxime intermediates and plants pesticidal compositions | |
JPH0651688B2 (ja) | 4.5―ジ置換1.3―チアゾル―2―イル―オキシアセタミド類 | |
US4130645A (en) | Fungicidal phenylnitramines and new phenylnitramines | |
EP0858446B1 (de) | Phenylcarbamate, verfahren und zwischenprodukte zu ihrer herstellung und ihre verwendung zur bekämpfung von schädlingen und schadpilzen | |
JPH02292257A (ja) | 3―シアノ―4―フエニル―ピロール誘導体類 | |
甲斐浩幸 et al. | Synthesis and fungicidal activity of 2-alkoxyimino-2-cyanoacetamide derivatives | |
JPH0688975B2 (ja) | 0−置換3−オキシピリジニウム塩及び該化合物を含有する殺菌剤 | |
JP3086316B2 (ja) | フェニルカーバメート誘導体、その製造法及び該誘導体を有効成分とする農園芸用殺菌剤 | |
JP2000086615A (ja) | フェニルカルバメ―ト、その製造及びその製造のための中間体、並びにこれらを含む組成物 | |
KR100501146B1 (ko) | 트리아졸 유도체, 그의 제조 방법 및 그를 포함하는농원예용 살균제 조성물 | |
KR0146504B1 (ko) | 아졸아미드 유도체 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |